CN106939064B - A kind of composition comprising perfluoropolyether active constituent - Google Patents
A kind of composition comprising perfluoropolyether active constituent Download PDFInfo
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- CN106939064B CN106939064B CN201611236769.9A CN201611236769A CN106939064B CN 106939064 B CN106939064 B CN 106939064B CN 201611236769 A CN201611236769 A CN 201611236769A CN 106939064 B CN106939064 B CN 106939064B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
- C09D183/12—Block or graft copolymers containing polysiloxane sequences containing polyether sequences
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
Abstract
The invention discloses a kind of compositions comprising perfluoropolyether active constituent, the composition includes: (1) at least one perfluoropolyether active constituent containing perfluoropolyether group and reaction active groups simultaneously, wherein the perfluoropolyether active constituent with comb-type structure accounts for 0.2% or more of active constituent gross mass;(2) the derivative hydrofluoroether of at least one tetrafluoroethene presents in an amount at least sufficient to dissolution or disperses the active constituent in (1).The one or more other activity for being dissolvable in water the derivative hydrofluoroether of tetrafluoroethene of the addition of being also an option that property of the composition and/or non-reactive additives ingredient, also may include the other cosolvent that can be dissolved each other with the derivative hydrofluoroether of tetrafluoroethene.The present invention can be used for substrate surface treatment, especially hard substrate such as optical glass, ceramics etc., have excellent anti-pollution function;The derivative hydrofluoroether of tetrafluoroethene is excellent to active constituent solubility property, and almost no three wastes generates in synthesis, safety and environmental protection.
Description
Technical field
The invention belongs to hard substrate surface soiling processing technology fields, and in particular to one kind comprising perfluoropolyether activity at
The composition divided.
Background technique
Perfluoropolyether active constituent is commonly used to carry out protective treatment to substrate, to obtain Water-proof and oil-proof and antifouling characteristic.
Such as the transparent optical device (such as mobile phone glass screen) of touch type electronic display device, it is often contacted with finger, is easy to be referred to
The pollution such as line, sweat, greasy dirt, device surface is after perfluoropolyether active constituent protective treatment, and dirt is without using solvent
In the case of can also facilitate removal, avoid the damage that may cause using solvent to display device, maintain the view of display device
Sense.Such as patent CN1284105 discloses a kind of antifouling coating composition for antireflective surfaces, patent CN101501046
Disclose a kind of composition of novel perfluoro polyether silicone, patent CN102666759 discloses a kind of for optical substrate
Surface treating composition.
But perfluoropolyether active constituent, which usually requires to be dissolved or dispersed in fluid media (medium), just can be carried out surface-treatment applications,
This relates to the material (being hereafter referred to as decentralized medium) for serving as carrier for active principle, diluent, decentralized medium or solvent.This point
Dispersion media should be able to promote transfer, transmission of the active constituent in expected use, have no effect on the effect of active constituent;Or at least
It should be able to promote transfer, the transmission of at least one active constituent, and not have a negative impact to the effect of active constituent.When making
Used time, since these decentralized media will be volatized into atmosphere, the environmental characteristics of decentralized medium material become to be increasingly subject to
Concern.It is a large amount of to make great efforts to be dedicated to exploitation to be 0 to ozone depletion potential (ODP) and to global warming potential between spending the more than ten years
(GWP) lesser decentralized medium material.In addition to having and to consider to be conducive to environmental characteristics, it is used as the material of decentralized medium further preferably
With relative to the inertia of one or more active constituents, hypotoxicity and low combustible.
Decentralized medium is needed come the coating layer of deposit perfluoro polyethers active component by the method for coating, optional dispersion is situated between
Aromatic hydrocarbon solvent (such as double-trifluoro of matter such as perfluocarbon (such as perflexane, PF 5070 and perfluorooctane), fluorine richness
Toluene), partially fluorinated hydrocarbon solvent (such as 2H, 3H- perflenapent) and hydrofluoroether etc..Typically, fluorination dispersion will be dissolved in
Very thin active constituent dope layer is generated in very dilute solution coating to substrate of active constituent in medium.Therefore,
A large amount of solvent is discharged into atmospheric environment.However, the big above-mentioned solvent in portion point is not 0 to ozone depletion potential (ODP), to the whole world
The potentiality (GWP) that warms is larger.
Perfluoro butyl methyl ether (7100) and perfluoro butyl ether (7200) ozone depletion potential (ODP) are 0, to global warming
Potentiality (GWP) is smaller, therefore is identified as the ideal dispersion medium of perfluoropolyether active constituent, patent CN1284105,
CN101501046 and CN102666759 etc. is all made of 7100 as decentralized medium.Secondly, perfluorobutyl methyl ethers and perfluoro butyl
Ethylether surface tension is low, viscosity is low, is easy to be formed in substrate surface processed and uniformly sprawl;But also there is evaporation latent heat
Advantage low, drying time is short avoids solvent and retains the destruction that may be generated to substrate for a long time;Its is non-combustible, is a kind of
On environment, there are few the environment-friendly type solvents of influence.However, perfluorobutyl methyl ethers and perfluorobutyl ethyl ether use electrofluorination work
Prepared by skill, can generate more waste in production technology complexity, preparation process.Thus its is at high cost, production environmental protection pressure is big.Mirror
In this, it is badly in need of searching and is readily produced, waste is not generated or generated less in production process and substitution solvent at low cost.
Summary of the invention
Above-mentioned technical problem present in present invention aims to solve the prior art provides a kind of living comprising perfluoropolyether
Property ingredient composition, using the derivative hydrofluoroether of tetrafluoroethene as decentralized medium, depletion of the ozone layer coefficient is zero, global greenhouse effect
Coefficient is also very low, almost has no adverse effects to environment;The derivative hydrofluoroether of tetrafluoroethene is readily produced, and production cost is low, thus
Greatly reduce the cost of composition;Compared with the perfluorobutyl methyl ethers of electrofluorination preparation, the derivative hydrofluoroether of tetrafluoroethene
The waste generated in production process is less;In addition, effect nothing of the derivative hydrofluoroether of tetrafluoroethene to perfluoropolyether active constituent
Adverse effect.
In order to solve the above-mentioned technical problem, the present invention adopts the following technical scheme:
A kind of composition comprising perfluoropolyether active constituent, it is characterised in that the composition includes:
(1) at least one perfluoropolyether active constituent containing perfluoropolyether group and reaction active groups simultaneously, wherein
Perfluoropolyether active constituent with comb-type structure accounts for 0.2% or more of active constituent gross mass;
(2) the derivative hydrofluoroether of at least one tetrafluoroethene presents in an amount at least sufficient to dissolution or disperses the active constituent in (1);The group
It adds one or more tetrafluoroethene that are dissolved in closing being also an option that property of object derives the other active and/or nonactive of hydrofluoroether
Additive component also may include the other cosolvent that can be dissolved each other with the derivative hydrofluoroether of tetrafluoroethene.
Further, the derivative hydrofluoroether of tetrafluoroethene is obtained by tetrafluoroethene and monohydric alcohol through addition reaction.
Further, the derivative hydrofluoroether of tetrafluoroethene is selected from HFE-347 (CF3CH2OCF2CF2H)、HFE-49 4n
(CH3CH2CH2OCF2CF2) and HFE-458 (HCF H2CF2CH2OCF2CF2One of H).
Further, the derivative hydrofluoroether of tetrafluoroethene is preferably HFE-347 (CF3CH2OCF2CF2H)。
Further, the perfluoropolyether active constituent simultaneously containing perfluoropolyether group and reaction active groups can use formula
(1) or formula (2) indicates:
(PFPE1-N)m-M-(K-Si(OR)3)nFormula (1),
((RO)3Si-K)s-I-PFPE2-I-(K-Si(OR)3)sFormula (2);
Wherein, PFPE1For monovalent perfluorinated polyether group, PFPE2For divalent perfluoropolyether, N and K are bivalent organic group, I
For s+1 valence organic group or covalent bond, M is m+n valence organic group, R C1~4Alkyl, m, n, s be positive integer;When m, n are equal
When for integer more than or equal to 2, that is, indicate the perfluoropolyether with comb-type structure.
Further, the perfluoropolyether active constituent in formula (1) simultaneously containing perfluoropolyether group and reaction active groups can
By monomer CH2=CR1-A-PFPE1And CH2=CR2-B-Si(OR′)3Through free-radical polymerized acquisition or by (CH3)3SiO(Si
(CH3)2O)x(Si(CH3)H)y+zSi(CH3)3Monomer CH with y moles respectively2=CHCH2 OCH2PFPE1With z moles of monomer
CH2=CH-E-Si (OR ')3It is obtained through Si―H addition reaction, wherein R1And R2For H or CH3, R ' is C1~4Alkyl, A be divalent it is organic
Group, B, E are covalent bond or bivalent organic group, PFPE1For monovalent perfluorinated polyether group, x is positive integer, and y, z are more than or equal to 2
Positive integer;PFPE can also be selected from1-CH2OCH2CH2CH2Si(OCH3)3、PFPE1-(OH)(CH2CH2CH2Si(OC H3)3)2Deng
One of.
Further, monomer CH2=CR1-A-PFPE1Selected from CH2=CHCH2OCH2PFPE1And CH2=C (CH3)
COOCH2PFPE1One of, monomer CH2=CR2-B-Si(OR′)3Selected from CH2=CHCH2Si(OCH 3)3And CH2=C (CH3)
COO CH2CH2CH2Si(OCH2CH3)3One of;Monomer CH2=CH-E-Si (OR ')3Selected from CH2=CHCH2Si(OCH3)3;
Wherein PFPE1For monovalent perfluorinated polyether group.
Further, it is selected simultaneously containing the perfluoropolyether active constituent of perfluoropolyether group and reaction active groups in formula (2)
From ((H3CO)3SiCH2CH2CH2)2NOC-PFPE2-CON(CH2CH2CH2Si(OCH3)3)2。
Further, the other activity and/or non-reactive additives ingredient original silicon of the derivative hydrofluoroether of tetrafluoroethene are dissolvable in water
Or mixtures thereof one of acetoacetic ester, methyltrimethoxysilane and perfluoro polyether oil.
The present invention is by adopting the above-described technical solution, have the advantages that
1) composition comprising perfluoropolyether active constituent of the invention is using the derivative hydrofluoroether of tetrafluoroethene as decentralized medium,
Depletion of the ozone layer coefficient is zero, and global greenhouse effect coefficient is also very low, is almost had no adverse effects to environment;
2) composition comprising perfluoropolyether active constituent of the invention is using the derivative hydrofluoroether of tetrafluoroethene as decentralized medium,
The derivative hydrofluoroether of tetrafluoroethene is excellent to active constituent solubility property, and the derivative hydrofluoroether of tetrafluoroethene is readily produced, production cost
It is low, to be greatly reduced the cost of composition;
3) the derivative hydrofluoroether production process of the tetrafluoroethene in the composition comprising perfluoropolyether active constituent of the invention
The waste of middle generation is less, i.e. raw material production also has the characteristics that safety and environmental protection;
4) the derivative hydrogen fluorine of the composition comprising perfluoropolyether active constituent of the invention decentralized medium tetrafluoroethene therein
Ether has no adverse effects to the effect of perfluoropolyether active constituent, and composition Water-proof and oil-proof and anti-pollution are excellent, can be used for substrate
Surface treatment, especially hard substrate such as optical glass, ceramics etc..
Specific embodiment
The present invention provides a kind of composition comprising perfluoropolyether active constituent, comprising: at least one contains perfluor simultaneously
The perfluoropolyether active constituent of polyether group and reaction active groups, wherein the perfluoropolyether active constituent with comb-type structure accounts for
0.2% or more of active constituent gross mass;The derivative hydrofluoroether of at least one tetrafluoroethene, present in an amount at least sufficient to dissolution or dispersion activity at
Point.The derivative hydrofluoroether of tetrafluoroethene has the low surface tension and viscosity for the perfluorobutyl ethyl ether that can compare, and is equally easy in quilt
Processing substrate surface, which is formed, uniformly to be sprawled;Also have the advantages that evaporation latent heat is low, drying time is short, it can be to avoid solvent for a long time
Retain the destruction that may be generated to substrate;Its non-combustible, depletion of the ozone layer coefficient is that 0, global greenhouse effect coefficient is very low, equally
It is a kind of pair of environment almost without dysgenic environment-friendly type solvent.Contain comprising the perfluoropolyether active constituent with comb-type structure
Perfluoropolyether group is easy to migrate to coating surface in the curing process, assigns coating excellent anti-pollution;Combed perfluor
Polyethers has higher molecular weight and a fairly large number of siloxane group, strong with substrate binding force, and it is resistance to further improve coating
Mill property and antifouling persistence;Uniform coating is more readily formed in combed perfluoropolyether and the mutual cooperation of other perfluoropolyether.The combination
The addition of being also an option that property of object is one or more to be dissolvable in water the other active and/or nonactive of the derivative hydrofluoroether of tetrafluoroethene
Additive component has certain adjustment effect for lubrication feel, the hardness of film etc. that improve combination coating.
The derivative hydrofluoroether of tetrafluoroethene of the invention is obtained by tetrafluoroethene and monohydric alcohol through addition reaction.Specific reaction equation
It is as follows:
F2C=CF2+HO-R→CHF2CF2OR
Monohydric alcohol HO-R can be listed below: CH3OH、CF3CH2OH、CH3CH2OH、CH3CH2CH2 OH、CH3CH(OH)CH3、
CH3OCH2CH2OH、CH3CH2CH2CH2OH、(CH3)2CH2CH2 OH、m-CH3-C6H4-OH、C6H5-CH2OH、HCF2CF2CH2OH etc..
The derivative hydrofluoroether HFE-254 (CH of tetrafluoroethene can be prepared by above-mentioned monohydric alcohol3OCF2CF2H)、HFE-347(CF3CH2O
CF2CF2H)、HFE-374(CH3CH2OCF2CF2H)、HFE-494n(CH3CH2CH2OCF2CF2H)、 HFE-494i((CH3)2CHOCF2CF2H)、HFE-494e2(CH3OCH2CH2OCF2CF2H)、HF E-5114n(CH3(CH2)3OCF2CF2H)、HFE-
5114i((CH3)2CHCH2OCF2CF2H)、HFE- 894m(m-CH3C6H4OCF2CF2H)、HFE-894Bz
(C6H5CH2OCF2CF2H), HFE-458 (H CF2CF2CH2OCF2CF2H) etc..Wherein be preferably HFE-347, HFE-494n and
One of HFE-458;Wherein it is more preferably HFE-347.With the perfluoro butyl methyl ether or perfluor prepared by electrofluorination method
Butyl ether is compared, and it is a kind of that generation waste is less in the derivative hydrofluoroether production process of tetrafluoroethene, and production environmental protection pressure is small
The ideal solvent environmentally friendly from producing to using.In addition, effect of the derivative hydrofluoroether of tetrafluoroethene to perfluoropolyether active constituent
It has no adverse effects.
Perfluoropolyether active constituent in the present invention simultaneously containing perfluoropolyether group and reaction active groups can use formula
(1) or formula (2) indicates
(PFPE1-N)m-M-(K-Si(OR)3)nFormula (1),
((RO)3Si-K)s-I-PFPE2-I-(K-Si(OR)3)sFormula (2).
Wherein, PFPE1For monovalent perfluorinated polyether group, PFPE2For divalent perfluoropolyether, N and K are bivalent organic group, I
For s+1 valence organic group or covalent bond, M is m+n valence organic group, R C1~4Alkyl, m, n, s be positive integer;When m, n are equal
When for integer more than or equal to 2, that is, indicate the perfluoropolyether with comb-type structure.
Perfluoropolyether active constituent in formula (1) simultaneously containing perfluoropolyether group and reaction active groups can be by monomer
CH2=CR1-A-PFPE1、CH2=CR2-B-Si(OR′)3And CH2=CR3-D-N(R′)2Through free-radical polymerized acquisition or by (CH3)3SiO(Si(CH3)2O)x(Si(CH3)H)y+zSi(CH3)3Monomer C H with y moles respectively2=CHCH2OCH2PFPE1With z moles
Monomer CH2=CH-E-Si (OR ')3It is obtained through Si―H addition reaction, wherein R1And R2For H or CH3, R ' is C1~4Alkyl, A bis-
Valence organic group, B, E are covalent bond or bivalent organic group, PFPE1For monovalent perfluorinated polyether group, x is positive integer, and y, z are
Positive integer more than or equal to 2;PFPE can also be selected from1-CH2OCH2CH2CH2Si(OCH3)3、PFPE1-(OH)(CH2CH 2CH2Si
(OCH3)3)2One of Deng.
Monomer CH in the present invention2=CR1-A-PFPE1Selected from CH2=CHCH2OCH2PFPE1、CH2=CHCO OCH2PFPE1
And CH2=C (CH3)COOCH2PFPE1One of.CH2=CHCH2OCH2PFPE1HOCH can be passed through2PFPE1With CH2=CH
CH2Br etherification reaction obtains, CH2=CHCOOCH2PFP E1And CH2=C (CH3)COOCH2PFPE1HOCH can be passed through2PFPE1
With CH2=CHCOOH or C H2=C (CH3) acquisition of COOH esterification.
Monomer CH in the present invention2=CR2-B-Si(OR)3It can be listed below: CH2=CHSi (OCH3)3、CH2=C HSi
(OC2H5)3、CH2=CH CH2Si(OCH3)3、CH2=CHCH2Si(OC2H5)3、CH2=CHCOO (C H2)3Si(OCH3)3、CH2=
CHCOO(CH2)3Si(OC2H5)3、CH2=CH (CH3)COO(CH2)3Si(OC H3)3、CH2=CH (CH3)COO(CH2)3Si
(OC2H5)3Deng can be one of which, be also possible to two kinds or more of mixture.It is wherein preferably CH2=CHCH2Si
(OCH3)3、CH2=CH Si (OCH2CH3)3And CH2=C (CH3)COOCH2CH2CH2Si(OCH2CH3)3One of.
Monomer CH in the present invention2=CR3-D-N(R′)2It can be listed below: CH2=CHCH2N(CH3)2、CH2=C HCH2N
(C2H5)2、CH2=CHCH2N(C3H8)2、CH2=C (CH3)COOCH2CH2N(CH3)2、CH 2=C (CH3)COOCH2CH2N
(C2H5)2、CH2=CHCOOCH2CH2N(CH3)2、CH2=CHCOOC H2CH2N(C2H5)2Deng, it can be one of which, it can also be with
It is two kinds or more of mixture.It is wherein preferably CH2=C (CH3)COOCH2CH2N(CH3)2And CH2=CHCH2N(CH3)2In
One kind.
Monomer CH in the present invention2=CH-E-Si (OR ')3Selected from CH2=CHCH2Si(OCH3)3And CH2=CHSi
(OCH2CH3)3One of;Wherein PFPE1For monovalent perfluorinated polyether group.
Perfluoropolyether active constituent containing perfluoropolyether group and reaction active groups in formula (1) can be listed below:
PFPE1-CONHCH2CH2CH2Si(OCH3)3、PFPE1-CON(CH2CH2CH2Si(OCH3)3)2、 PFPE1-CH2OCH2CH2CH2Si
(OCH3)3、PFPE1-CH2OCH2CH2CH2Si(OC2H5)3、PFPE 1-CH2OCH2CH2CH2Si(CH3)2OSi(CH3)2CH2CH2Si
(OCH3)3、PFPE1-CH2OCH2CH2C H2Si(CH2CH2CH2Si(OCH3)3)3、PFPE1-CONHCH
(CH2OCONHCH2CH2OOCCH2C H2N(CH2CH2CH2Si(OCH3)3)2)2、PFPE1-CH2OCH2CH2CH2Si(CH3)O(Si
(CH3)(CH2 CH2CH2Si(OCH3)3)O)2Si(CH3)(CH2CH2CH2Si(OCH3)3) O and comb-type structure perfluoropolyether.
Perfluoropolyether active constituent in formula (2) simultaneously containing perfluoropolyether group and reaction active groups can enumerate as
Under: (H3CO)3SiCH2CH2CH2NHOC-PFPE2-CONHCH2CH2CH2Si(OCH3)3、((H3 CO)3SiCH2CH2CH2)2NOC-
PFPE2-CON(CH2CH2CH2Si(OCH3)3)2、(H3CO)3SiCH2C H2CH2OCH2-PFPE2-CH2OCH2CH2CH2Si(OCH3)3。
PFPE in the present invention1It for monovalent perfluorinated polyether group, can be listed below: F (CF (CF3)CF2O)kCF(CF 3)-、F
(CF(CF3)CF2O)kCF2CF2-、CF3O(CF2CF2O)kCF2-、CF3O(CF2O)l(CF2CF2O)k CF2Etc., wherein k, l be 1 to
50 integer.
PFPE in the present invention2It for divalent perfluoropolyether group, can be listed below :-CF (CF3)O(CF(CF3)C F2O)kCF
(CF3)-、-CF2CF2(CF(CF3)CF2O)kCF2CF2-、-CF2O(CF2CF2O)kCF2-、-CF2 O(CF2O)l(CF2CF2O)kCF2-
Deng the integer that wherein k, l are 1 to 50.
The other activity and/or non-reactive additives ingredient that the derivative hydrofluoroether of tetrafluoroethene is dissolvable in water in the present invention can arrange
It lifts as follows: ethyl orthosilicate, methyltrimethoxysilane, methyltriethoxysilane, ethyl trimethoxy silane, isopropyl three
Methoxy silane, 3- r-chloropropyl trimethoxyl silane, 3- glycidoxypropyltrietandysilane andysilane, F (CF (CF3)CF2O)k
CF2CF3(wherein k is 10~60) etc., can be one of which, is also possible to two kinds or more of mixture.Wherein preferred former silicon
Or mixtures thereof one of acetoacetic ester, methyltrimethoxysilane and perfluoro polyether oil.
The raw materials used in the present invention is commercially available or is prepared, specific as follows:
A1:CH2=CHCH2Br;
A2:CH2=C (CH3)COOH;
C1:H3COOCCF(CF3)[OCF2CF(CF3)]30OCF2CF2CF3;
C2:H3COOCCF2O(CF2O)12.3(CF2CF2O)13CF2COOCH3;
C3:F (CF (CF3)CF2O)34CF2CF3;
C4:HOCH2CF(CF3)[OCF2CF(CF3)]30OCF2CF2CF3(NaBH is passed through by C14Reduction preparation);
S1:CH2=CHCH2Si(OCH3)3;
S2:CH2=C (CH3)COOCH2CH2CH2Si(OCH2CH3)3;
S3:Si (OC2H5)4;
S4:CH3Si(OCH3)3;
S5:NH (CH2CH2CH2Si(OCH3)3)2;
S6:(CH3)3SiO(Si(CH3)2O)35(Si(CH3)H)10Si(CH3)3;
S7:HSiCl3;
Y1: di-isopropyl peroxydicarbonate;
Decentralized medium: HFE-347;
(the monomer CH of synthesis example 12=CHCH2OCH2PFPE1Synthesis --- F1)
In the three-necked flask device for being equipped with reflux condensing tube and constant pressure funnel, 500gC4 and 1500m l HFC- is added
347,20%NaOH solution 80g is added under nitrogen protection as catalyst, rear addition 60g A1 back flow reaction 6 hours, uses water
Washing, vacuum distillation remove solvent and remaining water, obtain 510gF 1.
(the monomer CH of synthesis example 22=C (CH3)COOCH2PFPE1Synthesis --- F2)
In four mouthfuls of reaction flasks for being equipped with blender, constant temperature oil bath, thermometer and condenser be added 1000g C1,
The A2 of 45g, appropriate water entrainer and a small amount of hydroquinone polymerization inhibitor and a small amount of Catalyzed by p-Toluenesulfonic Acid agent, are warming up under stiring
120 DEG C of progress esterifications, until esterification finishes when water in separator is close to theoretical value.Then pass through air-distillation
It goes out water entrainer and unreacted A2 with vacuum distillation, then by washing away catalyst and polymerization inhibitor, is dried in vacuo respectively
To 1005gF2.
Synthesis example 3 (synthesis of combed perfluoropolyether E1)
In four mouthfuls of reaction flasks for being equipped with blender, constant temperature oil bath, thermometer and condenser be added 50gF1,
6.5gS1,0.5gY1 and 85g HFC-347, stirring are warming up to reflux temperature, react 15h, and infrared analysis double bond absorption peak disappears,
Appropriate HFC-347 is added, effective component is adjusted to 25%, obtains 25% solution of combed perfluoropolyether E1.
Synthesis example 4 (synthesis of combed perfluoropolyether E2)
In four mouthfuls of reaction flasks for being equipped with blender, constant temperature oil bath, thermometer and condenser be added 50gF 2,
10gS2,0.5gY1 and 90g HFC-347, stirring are warming up to reflux temperature, react 15h, and infrared analysis double bond absorption peak disappears,
Appropriate HFC-347 is added, effective component is adjusted to 25%, obtains 25% solution of combed perfluoropolyether E2.
Synthesis example 5 (synthesis of combed perfluoropolyether E3)
In the three-necked flask device for being equipped with reflux condensing tube and constant pressure funnel, 6 He of 20gS is added into constant pressure funnel
30gF1,5gS1 and 70ml HFC-347 are added into there-necked flask, is uniformly mixed by 20ml HFC-347, and chloroplatinic acid is added and urges
Agent 0.3g, is heated to reflux temperature, starts that S8 solution is slowly added dropwise, drips off within 30 minutes, reacts 15h, and infrared detection double bond is inhaled
It receives peak to disappear, adds appropriate HFC-347, adjust effective component to 25%, obtain 25% solution of combed perfluoropolyether E5.
(the perfluoropolyether siloxanes PFPE of synthesis example 61-CH2OCH2CH2CH2Si(OCH3)3Synthesis --- D1)
It is prepared by F1 and S7 Si―H addition reaction by alcoholysis referring to the method in patent CN103551075A synthesis example 1,
Then appropriate HFC-347 is added and adjusts effective component to 25%, obtains 25% solution of D1.
(the perfluoropolyether siloxanes PFPE of synthesis example 71-C(OH)(CH2CH2CH2Si(OCH3)3)2Synthesis --- D 2)
React preparation with allylic bromination magnesium by C1 referring to the method in patent CN104945610A synthesis example 1, then plus
Enter appropriate HFC-347 and adjust effective component to 25%, obtains 25% solution of D2.
(perfluoropolyether the siloxanes ((H of synthesis example 83CO)3SiCH2CH2CH2)2NOC-PFPE2-CON(CH2CH2C H2Si
(OCH3)3)2Synthesis --- D3)
Pass through the amidation process preparation of C2 and S5 that molar ratio is 1:2.Reaction carries out under nitrogen protection, and 85 DEG C anti-
Answer 5h.Suitable HFC-347 is added in product, adjusts effective component to 25%, obtains 2 5% solution of D3.
Examples 1 to 6
Quantitatively weigh each component, and be added in flask, stir evenly obtain it is of the invention comprising perfluoropolyether activity at
The composition divided.See Table 1 for details for specific formula.
Table 1
It is mass fraction in table 1;X in X/Y refers to that the number of decentralized medium, Y refer to the number of perfluoropolyether active constituent.
Stability refers to phenomena such as room temperature stands 1 month without being layered, precipitating.
Comparative example
Using with the identical perfluoropolyether active constituent formula of embodiment 1,4,6, by decentralized medium perfluoro butyl methyl
Ether (7100) substitution.
Base material treatment
Examples 1 to 6 is diluted to HFE-345 to 0.1% concentration, by comparative example with 7100 be diluted to 0. 1% it is dense
Degree, dilution is sprayed on mobile phone glass screen, and solidify 0.5h at 160 DEG C, forms nonpolluting coating.
Test method
1, contact angle test
Mobile phone glass screen Jing Guo antifouling process is subjected to deionized water (W) and white mineral oil (O) with contact angle instrument
Contact angle test.It is measured in parallel 5 times, is averaged.Contact angle is bigger, and surface can be smaller, and as a result see Table 2 for details.
2, antipollution assessment
Oil pen's test: drawing a line with oil pen on mobile phone glass screen film, then examines ink traces change
Change, and evaluated with following standard:
E: ink rapid desufflation,
F: ink portions are shunk,
NG: ink is not shunk substantially,
As a result see Table 2 for details.
3, dirt ease of removal is evaluated
The red oil-based dye that mass fraction is 3% is prepared, after picking sufficient amount with finger, by finger in mobile phone glass screen
Holding 5 seconds is forced with 1Kgf on film, the pressure of 1Kgf then is applied to non-dust cloth and is wiped fingerprint 5 times back and forth, with following
Standard is evaluated:
E: not leaving stain,
F: there are a small number of stains,
NG: there are most stains,
As a result see Table 2 for details.
Table 2
From table 2 it can be seen that the composition comprising perfluoropolyether active constituent of the invention use HFE-34 7 for point
After dispersion media, have no adverse effects to the performance of perfluoropolyether active constituent.
The invention has the following advantages:
1) composition comprising perfluoropolyether active constituent of the invention is using the derivative hydrofluoroether of tetrafluoroethene as decentralized medium,
Depletion of the ozone layer coefficient is zero, and global greenhouse effect coefficient is also very low, is almost had no adverse effects to environment.
2) composition comprising perfluoropolyether active constituent of the invention is using the derivative hydrofluoroether of tetrafluoroethene as decentralized medium,
Production cost substantially reduces.
3) the derivative hydrofluoroether production process of the tetrafluoroethene in the composition comprising perfluoropolyether active constituent of the invention
The waste of middle generation is less, i.e. raw material production also has the characteristics that safety and environmental protection.
4) the derivative hydrogen fluorine of the composition comprising perfluoropolyether active constituent of the invention decentralized medium tetrafluoroethene therein
Ether has no adverse effects to the effect of perfluoropolyether active constituent, and composition Water-proof and oil-proof and anti-pollution are excellent, can be used for substrate
Surface treatment, especially hard substrate such as optical glass, ceramics etc..
The above is only specific embodiments of the present invention, but technical characteristic of the invention is not limited thereto.It is any with this hair
Based on bright, to solve essentially identical technical problem, essentially identical technical effect is realized, made simple change, etc.
With replacement or modification etc., all it is covered by among protection scope of the present invention.
Claims (3)
1. a kind of composition comprising perfluoropolyether active constituent, it is characterised in that the composition includes:
(1) at least one perfluoropolyether active constituent containing perfluoropolyether group and reaction active groups simultaneously, wherein having
The perfluoropolyether active constituent of comb-type structure accounts for 0.2% or more of active constituent gross mass;
(2) the derivative hydrofluoroether of at least one tetrafluoroethene presents in an amount at least sufficient to dissolution or disperses the active constituent in (1);
The composition is added with one or more other activity and/or nonactive addition for being dissolved in the derivative hydrofluoroether of tetrafluoroethene
Agent ingredient, or other cosolvent comprising dissolving each other with the derivative hydrofluoroether of tetrafluoroethene, it is described to contain perfluoropolyether group simultaneously
It is indicated with the perfluoropolyether active constituent formula (1) or formula (2) of reaction active groups:
(PFPE1-N)m-M-(K-Si(OR)3)nFormula (1),
((RO)3Si-K)s-I-PFPE2-I-(K-Si(OR)3)sFormula (2);
Wherein, PFPE1For monovalent perfluorinated polyether group, PFPE2For divalent perfluoropolyether, N and K are bivalent organic group, I s+1
Valence organic group or covalent bond, M are m+n valence organic group, R C1~4Alkyl, m, n, s be positive integer;When m, n are to be greater than
When integer equal to 2, that is, indicate the perfluoropolyether with comb-type structure;And formula (1) it is described simultaneously containing perfluoropolyether group and
The perfluoropolyether active constituent of reaction active groups is by monomer CH2=CR1-A-PFPE1And CH2=CR2-B-Si(OR′)3Through freedom
Base copolymerization obtains or by (CH3)3SiO(Si(CH3)2O)x(Si(CH3)H)y+zSi(CH3)3Monomer CH with y moles respectively2=CH
CH2OCH2PFPE1With z moles of monomer CH2=CH-E-Si (OR ')3It is obtained through Si―H addition reaction, wherein R1And R2For H or CH3, R '
For C1~4Alkyl, A is bivalent organic group, and B, E are covalent bond or bivalent organic group, and x is positive integer, y, z be more than or equal to
2 positive integer;The monomer CH2=CR1-A-PFPE1Selected from CH2=CHCH2OCH2PFPE1And CH2=C (CH3)COOCH2PFPE1
One of, monomer CH2=CR2-B-Si(OR′)3Selected from CH2=CHCH2Si(OCH3)3And CH2=C (CH3)
COOCH2CH2CH2Si(OCH2CH3)3One of;Monomer CH2=CH-E-Si (OR ')3Selected from CH2=CH CH2Si(OCH3)3;
And formula (2) the perfluoropolyether active constituent simultaneously containing perfluoropolyether group and reaction active groups is selected from ((H3CO)3SiCH2CH2CH2)2NOC-PFPE2-CON(CH2CH2CH2Si(OCH3)3)2, the derivative hydrofluoroether of the tetrafluoroethene is selected from HFE-
347(CF3CH2OCF2CF2H)、HFE-494n(CH3CH2CH2OCF2CF2) and HFE-458 (HCF H2CF2CH2OCF2CF2H one in)
Kind.
2. a kind of composition comprising perfluoropolyether active constituent according to claim 1, it is characterised in that: the tetrafluoro
Ethylene derivative hydrofluoroether is preferably HFE-347 (CF3CH2OCF2CF2H)。
3. a kind of composition comprising perfluoropolyether active constituent according to claim 1, it is characterised in that: described solvable
Solution is ethyl orthosilicate, methyl trimethoxy oxygen in the other activity and/or non-reactive additives ingredient of the derivative hydrofluoroether of tetrafluoroethene
Or mixtures thereof one of base silane and perfluoro polyether oil.
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